Acidic esters of oxypropylated resorcinol



Patented May 25, 1954 UNITED STATES PATENT OFFICE ACIDIC ESTERS OF OXYPROPYLATED RESOROINOL Melvin De Groote,

ware

University City, Mo., assignor to Petrolite Corporation,

a corporation of Dela- No Drawing. Application May 14, 1951, Serial No. 226,331

10 Claims. (Cl. 260475) It includes methods or procedures for manufacturing said new chemicafproducts, compounds or compositions, as well as the products, compounds, or compositions themselves.

larly petroleum emulsions. application Serial No. 226,330, now Patent No. 2,626,928.

Said new compositions are fractional esters obtained from a polycarboxy acid and a diol ob- See my copending file-d May 14, 1951,

tained by the oxypropylation of resorcinol or an The ethers obtained from resorcinol and ethylene oxide suitable as reactants in preparing the herecompounds, may be indicated by the following formula:

with the proviso that m is a numeral varying from 0 to 4, and with the furthe proviso that the The manufacture of such hydroxy ethers is con ventional. If both phenolic hydroxyl radicals are converted into ethanol radicals, as is usually were used per pounds may be appropriately considered as glycol ethers.

For convenience, the hydroxylated compounds, 1. e., resorcinol itself, or the oxyethylated derivatives previously described, may be indicated by 2 the formula HOR'OH. Such products are soluble.

H(O CsHOnOR/O (CaHoOLuH with the proviso that n and 12/ represent whole numbers, which, added together, varying from 15 to 80', and the tained by reaction of the polycarboxy acid, be indicated thus:

and preferably free from any radicals having more than 8 uninterrupted carbon atoms in a single group, and with the further proviso that the parent diol, prior to esterification, be preferably water-insoluble and kerosene-soluble.

Attention is directed to the co -pending application of Charles M. Blair, Jr., Serial No.

a number of industrial applications, they are of particular value for resolving petroleum emul sions of the water-in-oil type that areof particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. This specific application is described and claimed in my copending a plication Serial No. 226,330, filed May 14, 1951, now Patent No. 2,626,928.

The new products are useful as wetting, detergents and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emul sifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

For convenience, what is said hereinafter will be divided into four parts:

Part 1 will be concerned with the oxypropylation of resorcinol or oxyethylated derivatives of the kind previously mentioned;

Part 2 will be concerned with the preparation of esters from the aforementioned oxypropylation derivatives Part 3 will be concerned with the structure of the herein described diols and its significance in light of what is said subsequently; and

Part 4 will be concerned with certain derivatives which can be obtained from diols of the type aforementioned.

PART 1 For a number of well known reasons, equipment, whether laboratory size, semi-pilot plant size, pilot plant size, or large scale size, is not, as

a rule, designed for a particular alkylene oxide.

Invariably, and inevitably, however, or particularly in the case of laboratory equipment and pilot plant size, the design is such as to use any of the customarily available alkylene oxides, i. e., ethylene oxide, propylene oxide, butylene oxide, glycide, epichlorohydrin, styrene oxide, etc. the subsequent description of the equipment it becomes obvious that it is adapted for oxyethylation, as well as oxypropylation.

Oxypropylations are conducted under a wide variety of conditions, not only in regard to presence or absence of catalyst, and the kind of catalyst, but also in regard to the time of reaction, temperature of reaction, speed of reaction, pressure during reaction, etc. For instance, oxyalkylations can be conducted at temperatures up to approximately 200 C. with pressures in about the same range up to about 200 pounds per square inch. They can be conducted also at temperatures approximating the boiling point of water or slightly above, as for example, 95 to 120 C. Under such circumstances, the pressure will be less than 30 pounds per square inch, unless some special procedure is employed, as is sometimes the case, to wit, keeping an atmosphere of inert gas such as nitrogen in the vessel during the reaction. Such low-temperature-low-reaction rate oxypropylations have been described very completely in U. S. Patent No. 2,448,664, to H. R. Fife et al., dated September 7, 1948. Low-temperature-low-pressure oxypropylations are particularly desirable where the compound being subjected to oxypropylation contains one, two, or three points of reaction only, such as monohydric alcohols, glycols and triols.

Since low-pressure-low-temperature-low-reaction-speed oxypropylations require considerable time, forinstance, 1 to '7 days of 24 hours each to complete the reaction, they are conducted, as a rule, whether on a laboratory scale, pilot plant scale, or large scale, so as to operate automatically. The prior figure of seven days applied especially to large-scale operations. I have used conventional equipment with two added automatic features: (a) a solenoid-controlled valve which shuts off the propylene oxide in event that the temperature gets outside a predetermined and set range, for instance, 95 to 120 C., and (b) another solenoid valve which shuts off the propylene oxide (or for that matter ethylene oxide if it is being used) if the pressure gets beyond a predetermined range, such as 25 to 35 pounds. Otherwise, the equipment substantially the same as is commonly employed for this purpose, where the pressure of reaction is higher, speed of reaction is higher, and time of reaction is much shorter. In such instances, such automatic controls are not necessarily used.

Thus, in preparing the various examples, I have found it particularly advantageous to use laboratory equipment or pilot plant which is designed to permit continuous oxyalkylation, whether it be oxypropylation or oxyethylation. With certain obvious changes, the equipment can be used also to permit oxyaikylation involving the use of glycide where no pressure is involved except the vapor pressure of a solvent, if any. which may have been used as a diluent.

As previously pointed out, the method of using propylene oxide is the same as ethylene oxide. This point is emphasized only, for the reason i that the apparatus is so designed and constructed as to use either oxide.

The oxypropylation procedure employed in the preparation of the oxyalkylated derivatives has been uniformly the same, particularly in light of the fact that a continuous,atomatically-controlled procedure was employed. In this procedure the autoclave was a conventional autoclave made of stainless steel and having a capacity of approximately 15 gallons and a working pressure of one thousand pounds gauge pressure. This pressure obviously is far beyond any requirement, as far as propylene oxide goes, unless there is a reaction of explosive violence involved due to accident. The autoclave was equipped with the conventional devices and openings, such as the variable-speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. M.; thermometer well and thermocouple for mechanical thermometer; emptying outlet; pressure gauge, manual vent line; charge hole for initial reactants; at least one connection for introducing the alkylene oxide. such as propylene oxide or ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave, such as a cooling jacket, and preferably,

tainer consists essentially of a laboratory bomb having a capacity of about one-half gallon, but

the rupture disc, pressure gauge, sight feed glass, thermometer connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use. The connections between the bomb and the autoclave were flexible stainless steel could be made without breaking or making any connections. This applies also to the nitrogen line which was used to pressure the bomb reservoir. To the extent that it was required, other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass protective screens, etc.

Attention is directed again to what has been mined range, or if pressure in the passes out of predetermined range.

With this particular arrangement practically all oxypropylations become uniform, in that the reaction temperature was held within a few de C. Numerous reactions were conducted in which the time varied from one day (24 hours) up to three days (72 hours), for completion of the final member of a series. In some instances, the reaction may take place in considerably less time, i. e., 24 hours or less, as far as a partial oxypropylation is concerned.

The minimum time recorded in subsequent data is about 8 hours. The reactions indicated as being complete in 8 to 10 hours, for example,

selected period; instance, if the selected period was 8 hours, the rate was set so the oxide could be fed in in about 5 hours, or less. This meant that if the reaction were interrupted automatically for a period of time for the pressure to drop or the temperature to drop, the predetermined amount of oxide quite a marked degree.

When operating at a comparatively high temperature, for instance, between 150 to 200 0., an unreacted alkylene oxide such as propylene oxide, makes its presence felt in the increase in pressure or the consistency of a higher pressure.

steps must be taken to safeguard against this possibility; if need be, a sample must be withdrawn and examined for unreacted propylene oxide.

pylate at a modestly higher temperature, for instance, at to C. Unreacted oxide affects determination of the acetyl or hydroxyl value of the hydroxylated compound obtained.

The higher the molecular weight of the comamount of oxide. One possible explanation is that the molecule, being larger, the opportunity for random reaction is decreased. Inversely, the lower the molecular weight, the faster the reaction takes place. For this reason, sometimes at least, increasing the concentration of the catalyst does not appreciably speed up the reacmaterials.

In a number of operations the counterbalance scale or dial scale holding the propylene oxide bomb reaction, the scale movement through a time operating device was set for either one to two hours, so that reaction continued for 1 to 2 hours after the final addition of the last propylene oxide, and thereafter the operation was shut down. This particular device is particularly suitable for use on larger equipment than laboratory size autoclaves, to wit, on semi-pilot plant or pilot plant size, as well as on large scale size. This final stirring period is intended to avoid the presence of unreacted oxide.

In this sort of operation. of course, the temperature range was controlled automatically by either use of cooling water, steam, or electrical heat, so as to raise or lower the temperature. The pressuring of the propylene oxide into the reaction vessel was also automatic, insofar that the 7 feed stream was set for a slow, continuous runwhich was shut off in case the pressure passed a predetermined point, as reviously set out. All the points of design, construction, etc., were conventional, including the gauges, check valves and entire equipment. As far as I am aware, at least two firms, and possibly three, specialize in autoclave equipment, such as I have employed in the laboratory, and are prepared to furnish equipment of this same kind. Similarly, pilot plant equipment is available. This point is simply made as a precaution in the direction of safety. Oxyalkylations, particularly involving ethylene oxide, glycide, propylene oxide, etc., should not be conducted except in equipment specifically designed for the purpose.

Example 1a The dihydroxy compound employed was resorcinol of technical purity. The autoclave employed was a small autoclave having a capacity of approximately one gallon. The autoclave was equipped with various automatic devices. In some instances, in similar oxypropylations employing either resorcinol or the oxyethylated derivatives of the kind previously described, the oxypropylations were speeded up and manual control used entirely. In this example, and in Examples 2a through 401., following, the automatic devices were employed. Needless to say, material in which way the autoclave is handled.

200 grams of resorcinol were charged into the autoclave along with grams of caustic soda. It is to be noted that other alkaline catalysts of the conventional type, such as sodium methylate, caustic potash, etc., would be equally satisfactory. The reaction pot was flushed out with nitrogen, the autoclave was sealed and the automatic devices adjusted for injecting 1620 grams of propylene oxide in approximately 8 hours. The pressure regulator was set for a maximum of pounds per square inch. This meant that the bulk of the reaction could take place and probably did take place at a comparatively lower pressure. This comparatively lower pressure was the result of the fact that, at least in part, considerable catalyst was present. The propylene Composition Before Oxide Catait is ima Theo.

that the amount of was increased in proportion. The amount of resorcinol employed was grams. The amount of propylene oxide employed was 1720 grams. The amount of catalyst employed was 10 grams. The conditions of reaction, as far as temperature and pressure were concerned, were identical with those described in Example 1a, preceding. The oxide was added somewhat more slowly, due, in part, to a lower catalyst concentration. The rate of addition was about 100 to 200 grams per hour. The time required to add the propylene oxide was 11 hours.

In this instance also when the oxypropylation was complete, the entire mass was saved for subsequent esterification.

Example 3a.

The procedure followed was identical with that used in Example la, preceding. The amount of resorcinol employed was '70 grams; the amount of propylene oxide employed was 1850 grams; the amount of catalyst employed was 7 grams. The conditions, as far as temperature and pressure were concerned, were identical with Examples 1a and 2a, preceding. The time period was longer, to wit, 16 hours. The addition rate of oxide was about 150 grams per hour. The entire reaction mass was saved for subsequent esterification.

Example 4a The same procedure was employed as in the three previous examples. The amounts of resorcinol employed was 50 grams; the amount of propylene oxide employed was 1775 grams; amount of catalyst employed was 5 grams. Conditions of temperature and pressure were the same as in the three previous examples. The reaction time was somewhat longer, to wit, 20 hours. The addition rate of oxide varied from to grams per hour. The entire reaction mass was retained for subsequent esterification.

What has been said herein is presented in tabular form in Table 1 immediately following, with some added information as to molecular weight and as to solubility of the reaction product in water, xylene and kerosene.

TABLE 1 Composition at end M.

by Max Pres, Time, 11.0 gage nt 533, 3 3" lbs. hrs.

In m ys s in. lbs. s. mm q 1, 020 20 866 115 as a 1,120 10 1, 020 115 35 11 1,850 7 1,845 115 35 10 1, 77s a 1,100 115 35 2o 1 The hydroxylated compound is resorcinol.

The same procedure was employed as in Exintroduction 866 compared with a theoretical xylene-soluble Example la was emulsiflable in water, soluble in xylene but insoluble in kerosene. Examples 2, 3a and 40. were all insoluble in water, but soluble in both xylene and kerosene.

Following the sam procedure, and this applies also to derivatives of resorcinol treated with 1, 2, 3 or 4 moles of ethylene oxide, I have made series in which the theoretical molecular weight, assuming completeness of reaction, has been at least twice as high as indicated in the above table, for instance, in the range of 8,000 to 10,000, and the hydroxyl molecular weight has been in the rang of 2,000 to 3,000. In all instances, the products were water-insoluble, and

and kerosene-soluble.

The final products, 1. e., at the end of the oxy- 10' propylationstep, were somewhat viscous, amberone, more opening to permit the use of a porous colored fluids which were water-insoluble. This spreader, if hydrochloric acid. gas: isto be used was characteristic of all various end products as acatalyst. Suchdevice or absorption spreader obtained in these series. These products were, consists of minute alundum thimbles which are caustic soda employed. This would be the case acid such as para-toluene sulfonicacid as-a catasimply by shaking small amounts or" themateria-ls 10 ar the oxypropylated compounds, and par- Weigh calcu ated by usu l met d of acetyl there is no reasonably convenient means availstoichiometrical amount of acid or acid com- The products obtained in Part 1, preceding,

'terof common knowledge and requires no further 35 t required t neutralize th residual maleic acid or a ydride adducts as obtained 50 the like, so-thatone has obtained approximately also if sodium methylate were used as a catalyst. lyst. There is some objection. to this because, Sp o inselllbility n W t r l li y in some instances, there is some evidence that in kerosene, u o u ty est ca be made this acid catalyst tends to decompose or rein a test tube with water present, for instan e. ticularly likely to do so if the esterification using 1% t0 5% app oxima y based 0 t temperature is too high. In the case of polyamount of water present. cal-boxy acids such as diglycolic acid, which is Needless to say, there is no complete conversion strongly acidic, there is no need to add any cata- Of P py OXide o the d d hyd y a 15 lyst. The use of hydrochloric. acid gas has one Compounds This is indicated y the feet that advantagev over para-toluene sulfonic acid, and the t o l m cu a W hesed 011 a that is, that at the end of the reaction it can be statistical average, is greater than the molecular removed by flushing out with nitrogen, whereas,

hydroxyl va ue. Actua y. there s n p t y able or removing the. para-toluene sulfonic acid at c y m d fo d e m molecule! or other sulfonic acid employed. If hydrochloric W i hts of these types of compound Wi h a high acid is employed, one need only pass the gas de r e of a cu When the molecular Weights through at an exceedingly slow rate so as to keep or hyd oxyl value serves s satisfactorily s an needs be present. I have employed hydrochloric ndex o the molecular Weight as y Other p acid gas or the aqueous acid itself to eliminate cedure, subject to the abov limitations, and the initial basic material. My preference, howe p y in the higher molecular Weight rangeever, is to use no catalyst whatsoever and to If y lty is encountered in the manufacinsure complete dryness of the diol, as described ture of the esters, as described in Part 2, the in the final procedure just preceding Table 2'.

elaboration. In fact, it is illustrated by some of gata,lyst The tu i h k th r hl and the e amples pp a in n t e pa previously allowed to stand overnight. It is then filtered mentionedand refluxed with the xylene present until the 2 water can be separated in a phase-separating trap. As soon as: the product is substantially free As previously pointed out, the present invenfrom water the distillation stops. This pretion is concerned with acidic esters obtained from liminary step can be carried out in the flask to the o yl opylated derivatives described in Part be used for esterification. If there is any further p ularly tr carboxy acids like citric and distage, needless to say, a second filtration may be by the Diels-Alder reaction from products such a 45% solution. To this solution there is added as male c a yd d and eyclopelltadiene- S at polycarboxylated reactant, as previously deacids should be heat-stable, so they are not described, such as phthalic anhydride, succinic acid mp d durin esterification. They may conor anhyd'ride, diglycolli'c acid, etc. The mixture tain as m ny a 3 carbon ms, a for xis refluxed until esterification is complete, as amp the a ds tain d y dim ti n f u indicated by elimination of water or drop in carsaturat d fatty a s u d m a xy boxy-I value. Needless to say, if one produces a in the hereto ap ded a m obv us y nc ud it is obtained from diglycollic acid for example,

the anhydrid s r any other v us qu v s water 15 eliminated All such procedul es are cony Preference, however, is to use p y rboxy ventional and have been so thoroughly described acids havin n r 8 carbon atoms in the literature that further consider atlon will The production of esters including d esters beliml'tedtoa few examples and a comprehensive (fractional esters) from polycarboxy acids and t bl ly ls or oth r hydr xyl ted omp unds is well other procedures for eliminating the basic known. Need ss t say. Various Compounds m y residual catalyst, if any, can be employed. For he used, such as the low molal ester, the anexample, the oxyalkylation can be conducted in hydride, the acyl chloride, etc. However, for absence of a solvent, or the solvent removed after purpose of economy, it is customary to use either oxypropylation. Such oxypropylation end prodthe acid or the anhydride. A conventonal pronot can then be acidified with just enough conamber liquid so obtained may contain a small to centrifugal drated sodium 6. then subject the mass eliminate the hysodium The clear, somewhat viscous,

amount of sodium sulfate or sodium chloride, but

in any event, is per cation in the manner It is to be pointed ou described are there is a plurality of both diol radicals; the product is charac described.

only one diol radical.

In some instances,

s in the sense that radicals and acid terized by having fectly acceptable for esterifit that the products here not polyester 2 40 m1., 234' c. 90 m1., 280 0. l 45 m1., 237 c. 95 m1., 307 c.

After this material is added, refluxing is continued, and, of course, is at a high temperature, to wit, about 160 to 170 C. If the carboxy reactant is an anhydride, needless to say, no water of'reaction appears; it the carboxy reactant is an acid water of reaction should appear and should be eliminated at the above reaction temperature. If it is not eliminated, I simply separate out another or 20 cc. of benzene by means of the phase-separating trap, and thus raise the temperature to 180 to 190 C. or even to 200 C.,

and in fact, in many if need be M reference is not to 0 above stances, I have found that in spite of the dehy- C. y p g dratlon method? employed above. that a mere The use of such solvent is extremely satisfactrace of water still comes through and that this tory, provided one does not attempt to remove mere trace of water certainly interferes with the the solvent subsequently, except by vacuum acetyl or hydroxyl value determination, at least nation, and provided there is no objection to when a number of t t are a little residue. Actually, when these materials used and y retard esttnficfa'tmnr Partlculafly are used for a purpose such as demulsification, where there 15 no sulfonic acid or hydrochloric the Solvent might just as well be allowed to acld present as a catalyst, Therefore, I have main. If the solvent is to be removed by distillaterrid to use the tonowmg procedmfei I have 0 tion, and particularly vacuum distillation, then oyeft about 200 graims'of the (11014 as 20 the high boiling aromatic petroleum solvent Z m g precedmg- I have added abqut might well be replaced by some more expensive t grams of enzene, and then refluxed h s solvent, such as decalin, or an alkylated decalin m the t resm F phase'sepa' which has a rather definite or close range boilrating trap until the benzene carried out all the m point-h The removal of the Solvent, of course, water present as water of solution or the equivais purely a conventional procedure and requires lent. Ordinarily, this refluxing temperature is no elaboration apt to be in the neighborhood of 130 to 1100- In the appended table Solvent #7-3, which apslbtyblto When an tttls water 9 pears in numerous instances, is a mixture of '7 has een removed, I also wtthdraw approxlmatevolumes of the aromatic petroleum solvent prety 20 grams or httle less benzene and then add viously described and 3 volumes of benzene. Re!- the required amount of the carboxy reactant and erence to solvent means t m also about 150 grams of mgh boflmg ammatlc troleum solvent previously described in detail. petroleum solvent. These solvents are sold by This was used, or a similar mixture, in the 9 refinenes' as tar as solvent ner previouesly described. A large number of 1:511 015ml; cilie y vgsreijlinfittgifli pl t 0 53 40 th examples indicated employing decalin were p a s 1 a ton a a m e repeated, using this mixture, and particularly pattmutar type I have employed and found Very with the preliminary step of removing all the Sattstactory are the touowmgt water. If one does not intend to remove the sol- I.B.P.,142 C. m1., 242 C. vent, my preference is to use the petroleum sol- 5 m1., 200 C. m1., 244 C. 45 vent-benzene mixture, although obviously any of 10 m1., 209 C. ml., 248 C. the other mixtures, such as decalin and xylene, 15 m1., 215 C. m1., 252 C. can be employed. 20 m1., 216 C. '70 m1., 252 C. The data included in the subsequent tables, 25 m1., 220 C. '75 m1., 260 C. i. e., Tables 2 and 3, are self-explanatory, and 30 m1., 225 C. m1., 264 C. 50 very complete, and it is believed no further elabo- 35 m1., 230 C. m1., 270 C. ration is necessary.

TABLE 2 M 1. Ex No. Theo T12? Actual W td Amt. of RE- dmxy W of droxyl gg zif Polycarboxy Reactant lggggggt d. H O of H 0 Value efistigil (grs.) (gm) 1,000 112.5 800 208 Dlglycolllc .4010 04.2 1,000 112.5 180 866 202 Ox Acid 58.4 1,000 112.5 130 865 197 Maleic Anhydride..- 44.5 1,000 112.5 866 211' Phthallc Anhydrlde... 72.0 1,000 112.5 130 806 201 Citraconic Anhydrlde. 51.8 1,000 112.5 130 800 210 20011101011010 88.0 2,000 50.1 74.0 1,520 210 Dlglycollic 401d 37.0 2,000 50.1 74.0 1,520 211 02011014010 35.0 2,000 50.1 74.0 1,520 218 Ma1eicAn11ydildc 28.0 2.000 50.1 74.0 .520 100 Phthalic Anhydride... 38.4 2, 000 56.1 74.0 1,520 209 Cltraconic Anhydrlde 30.9 2,000 50.1 74.0 1,520 48.0 3,020 37.2 01.0 1,845 20.4 3,020 37.2 01.0 1, 845 20.2 3,020 37.2 01.0 1,845 22.2 3,020 37.2 01.0 1,845 32.0 3,020 37.2 01.0 1,845 22.8 3,020 37.2 01.0 1,845 30.1 4, 020 28.0 04.0 1, 700 32.1 4,020 28.0 04.0 1,700 20.0 4, 020 28.0 04.0 1,700 22.2 4, 020 28.0 04.0 1, 700 33.8 4, 020 28.0 04.0 20.2

TABLE 3 Esterifig g gi cation Water (gm) T3151) Out (cc) ated by preceding examples. If, for any reason, reaction does not take place in a manner that is acceptable, attention should directed to the following details:

(a) Recheck the hydroxyl or acetyl value of the diol and use a stoichiometrically equivalent if need be; (c) If necessary, use fonic acid or some other acid as a catalyst;

tainin-g complete esterification.

Even under the most carefully controlled conditions of oxypropylation involving comparative propylene-oxide or derivatwes thereof, i. e., of an aldehyde, ketone, or allyl alcohol.

Even the determination of the hydroxyl value and conventional procedure leaves much to be desired, due either to the cogeneric materials 14 previously referred to, or, for that matter, the presence of any inorganic salts or propylene oxide. oxide should be eliminated.

The solvent employed, if any, can be removed from the finished ester by distillation, and particularly vacuum distillation. The final products or liquids are generally dark amber to amber in color, and show moderate viscosity. They can be bleached with bleaching clays, filtering chars, and

colorization is not justified.

In the above instances'I have permitted the solvents to remain present in the final reaction mass. In other instances, I have followed the using decalin or a mixture of decalin or benzene in the same manner .and ultimately removed all the solvents by vacuum distillation. Appearances of the final products are much the same as the diols :before esterification, and in some instances, were er in color and haps somewhat more viscous.

PART 3 Previous reference has that iols such as polypropylene herein described products and such comparable products appears to be rather insignificant. In fact, the difference is such that it fails to explain the fact that compounds of the kind herein described may be, and frequently are, 10%, 15%, or 20% better on a quantitative basi than the simpler compound previously described, and demulsify faster and give cleaner oil in many instances. The method of making such comparative tests has been described in a booklet entitled Treating Oil Field Emulsion, used in the Vocational Training Courses, Petroleum Industry Series, of the American Petroleum Institute.

The difierence, of course, does not reside in the Momentarily an ondary alcohol groups are united or a secondary alcohol group is united to a primary alcohol group, etherization being involved, of course, in each instance.

Usually, no effort is made tween oxypropylation taking mixture of closely logues. These materials invariably have high molecular weights and cannot be separated from one obtains products in basis, of course, 11. can be appropriately specified.

For practical purposes, one need only consider the oxypropylation of a monohydric alcohol, because, in essence, this is substantially the mechanism involved. Even in such instances where one is concerned with a monohydric reactant one cannot draw a single formula and say that by following such procedure one can readily obtain 80% or 90% or 100% of such compound. However, in the case of at least monohydric initial reactants one can readily draw the formulas of monohydric initial reactant, it is obvious that if one selects any such simple hydroxylated compound and subjects such compound to oxyalkylation, such as oxyethylation, or oxypropylation, it becomes obvious that one is really producing a polymer of the alkylene oxides, except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent, which, for the sake of convenience, may be indicated as RO(C2H4O')30OH. Instead, one obtains a cogeneric mixture of closely related homologues, in which the formula may be shown as the following, RO(C2H4O)nH, wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where 11. may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous com- Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to makethe product under consideration and how to repeat such production time after time without difiiculty, it is necessary to resort to some other method of description, or else consider the value of n, in formulas such as those which have appeared previously and which appear in the claims, as representing both individual constituents in which n has a single definite value, and also with the understanding that n represents the average statistical value based on the assumption of completeness of reaction.

This may be illustrated as follows: Assume that in any particular example, the molal ratio of the propylene oxide to the diol is to 1. Actually, which n probably varies made and such 516 from 10 to 20, perhaps even further. The average value, however, is 15, assuming, as previously stated, that the reaction is complete. The product described by the formula is best described also in terms of method of manufacture. However, in the instant situation it becomes obvious that if an ordinary high molal propylene glycol is compared to strings of white beads of various lengths, the diols herein employed as intermediates, are characterized by the presence of a black bead, i. e., a radical which corresponds to the radical derived from resorcinol or oxyethylated resorcinol, as previously described.

Furthermore, it becomes obvious now that one has a non-symmetrical radical in the majority of cases, for the reason that in the cogeneric mixture going back to the original formula:

(H0OC),."RH1(OCaHt),.0RO(C3HuO),' R(CO0H),." n and n are usually not equal. For instance, if one introduces 15 moles of propylene oxide, 11. and n could not be equal, insofar that the nearest approach to equality is where the value of n is '7 and n is 8. However, even in the case of an even number such as 20, 30, 40, or 50, it is also obvious that n and n will not be equal in light of what has been said previously. Both sides of the molecule are not going to grow with equal rapidity, i. e., to the same size. Thus, the diol herein employed is differentiated from polypropylene diol, 2,000, for example, in that (a) it carries a heterogeneous unit, i. e., a unit other than a propylene glycol or propylene oxide unit, (b) such unit is off center, and (c) that unit, of course, must have some efiect in the range with which the linear molecules can be drawn together by hydrogen binding or van der Waals forces, or whatever else may be involved.

Furthermore, in the present instance, due to the initial raw material employed, 1. e., an aromatic material, there is a ring structure present, 1. e., a phenyl radical which is not present in the polypropylene glycol.

What has been said previously can be emphasized in the following manner: It has been pointed out previously that in the last formula immediately preceding, n or n could be zero. Under the conditions of manufacture, as described in Part 2, it is extremely unlikely that n is over zero. However, such compounds can be prepared readily with comparatively little difficulty by resorting to a blocking effect or reaction. For instance, if a diol prepared as previously described is esterified with a low molal acid such as acetic acid, mole for mole, and such product subjected to oxyalkylation, using a catalyst, such as sodium methylate, and guarding against the presence of any water, it becomes evident that all the propylene oxide introduced, for instance, 15 to molecules per polyhydric alcohol, necessarily must enter at one side only. such product is then saponified so as to decompose the acetic acid ester, and then acidified so as to liberate the water-soluble acetic acid and the water-insoluble diol, a separation can be diol then subjected to esterification, as described in Part 2, preceding. Such esters, of course, actually represent products where either n or n is zero. Also, intermediate procedures can be employed, i. e., following the same esterification step after partial oxypropylation. For instance, one might oxypropylate with one-half the ultimate amount of propylene oxide to be used and then stop the reaction. One could then convert this partial oxypropylated intermediate into an ester by reaction of one mole of acetic acid with one mole of diol. This ester could then be ogypropylated with all the remaining propylene oxide. The final product so obtained could be saponified and acidified so as to eliminate the water-soluble acetic acid and free the obviously unsymmetrical diol, which, incidentally, should also be kerosene-soluble.

From a practical standpoint I have found no advantage in going to this extra step, but it does emphasize one of the differences in structure between the hereindescribed diols employed as intermediates and high molal polypropylene glycol, such as polypropylene glycol 2,000.

PART 4 As pointed out previously, the final product obtained is a fractional ester having free carboxyl radicals. Such product can be used as an intermediate for conversion into other derivatives which are eifective for various purposes, such as the breaking of petroleum emulsions of the kind herein described. For instance, such product can be neutralized with an amine so as to increase its water-solubility such as triethanolamine, tripropanolamine, oxyethylated triethanolamine, etc. Similarly, such product can be neutralized with some amine which tends to reduce the water-solubility such as cyclohexylamine, benzylamine, decylamine, tetradecylamine, octadecylamine, etc. Furthermore, the residual carboxyl radicals can be esterified with alcohols, such as low molal alcohols, methyl, ethyl, propyl, butyl, etc., and also high molal alcohols, such as octyl, decyl, cyclohexanol, benzyl alcohol, octadecyl alcohol, etc. Such products are also valuable for a variety of purposes, due to their modified solubility. This is particularly true where surface-active materials are of value, and especially in demulsification of water-in-oil emulsions.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

1. Hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

H II (HOOC),.-RC(O o3H@),.oR'0(OaHo ,.'oR o0011),. in which R a member selected from the class consisting of and o (C2H40)mH with the proviso that m is a numeral varying from to 4, and with the further proviso that the sum of both occurrences of m is not over 4, and not more than one occurrence of m is 0; n and n are numerals with the proviso that 'n and 11/ equal a sum varying from 15 to 80, and n" is a whole number not over 2, and R is the radical of a polybasic acid having not over 8 carbon atoms and composed of carbon, hydrogen and oxygen of the formula:

COOH

in which n" has its previous significance.

is the divalent radical obtained from proviso that n and n 15 to 80, and n" 2. Hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

(HOOC)n"R( (OC3Hs),.OR'O(C3HaO)n' R(COOH)n" in which R is the divalent radical obtained from resorcinol; n and n are numerals with the equal a sum varying from is a whole number not over 2,

bon, hydrogen and oxygen of the formula:

COOH in which n has its previous significance.

4. Hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

(HOOC),."R( (OC3Ht)nORO(CaHsO)' R(COOHLW in which R is the divalent radical obtained from resorcinol; n and n are numerals with the proand 11. equal a sum varying from 15 n" is a whole number not over 2, and

over 8 carbon atoms and composed of carbon,

formula:

coon

00011)." in which n has its previous significance; said polycarboxy acid having not over 8 carbon atoms.

5. Hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

(HOOC)R (0C3H6)nOR O(O3HdO)n' R(CO0H) in which R is the divalent radical obtained from resorcinol; n and n are numerals with the proviso that n and n equal a sum varying from 15 to and R is the radical of the dicarboxy acid OOOH R cooH said dicarboxy acid having not over 8 carbon atoms.

6. The product of claim 5, wherein the dicarboxy acid is phthalic acid.

7. The product of claim 5, wherein the dicarboxy acid is maleic acid.

8. The product of claim 5, wherein the dicarboxy acid is succinic acid.

9. The product of claim 5, wherein the dicarboxy acid is citraconic acid.

10. The product of claim 5, wherein the dicarboxy acid is diglycollic acid.

No references cited. 

1. HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING CHARACTERIZED BY THE FOLLOWING FORMULA: 